US5350504A - Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts - Google Patents

Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts Download PDF

Info

Publication number
US5350504A
US5350504A US07992668 US99266892A US5350504A US 5350504 A US5350504 A US 5350504A US 07992668 US07992668 US 07992668 US 99266892 A US99266892 A US 99266892A US 5350504 A US5350504 A US 5350504A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
process
feed
recited
aromatic
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US07992668
Inventor
Ralph M. Dessau
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
ExxonMobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44Hydrogenation of the aromatic hydrocarbons
    • C10G45/46Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/54Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44Noble metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium

Abstract

Non-acidic tin-, lead-, or indium-modified Pt/ZSM-5 catalysts are effective catalysts for the shape selective preferential hydrogenation of certain aromatic hydrocarbons in admixture with others. These catalysts can be used to reduce the aromatic content of gasoline and distillates.

Description

FIELD OF THE INVENTION

This invention relates to a process for selectively hydrogenating certain aromatic components in a mixture of aromatics based on molecular size which are contained in a gasoline or distillate pool of a petroleum refinery. It also provides a method for increasing the octane rating of the gasoline by-product from a hydrofinishing process.

BACKGROUND OF THE INVENTION

The demand for gasoline as a motor fuel is one of the major factors which dictates the design and mode of operation of a modern petroleum refinery. The gasoline product from a refinery is derived from several sources within the refinery including, for example, gasoline from the catalytic cracking unit, straight run gasoline, reformate and gasoline obtained as a low boiling by-product from various refinery operations, especially catalytic processes such as catalytic dewaxing. The octane number of the gasoline from these different sources varies according to the nature of the processing and the octane rating of the final gasoline pool will depend upon the octane ratings of the individual components in the pool as well as the proportions of these components. The increasing use of unleaded gasoline coupled with increasing engine efficiencies in road vehicles has led to a demand for increased gasoline pool octane which, in turn, makes it desirable to increase the octane values of the individual components of the pool. Although there are various ways of achieving this objective, some necessarily involve compromises which may render them less attractive in a commercial refinery operation. For example, the octane rating of FCC gasoline may be improved by operating the cracker at a higher temperature (conventionally measured at the top of the riser). Similarly, reformate octane may be increased by operating the reformer at higher severity. However, in both cases, a yield loss will ensue.

In the case of by-product gasoline from catalytic dewaxing processes it may be possible to improve octane during the start-up by increasing the temperature rapidly to a value higher than normal, as described in U.S. Pat. No. 4,446,007 (Smith). However, the use of higher temperatures in dewaxing processes will also tend to decrease the yield of dewaxed products. Alternative measures for increasing pool octane are therefore still desirable.

Another trend which is perceptible in the petroleum refining industry is towards the reduction of benzene and other lower boiling point aromatics in the gasoline or distillate pool. In the United States, the Environmental Protection Agency (EPA) is considering regulation of the gasoline content and similar measures are being considered in the European Community. Benzene is particularly prevalent in reformer gasoline, being a distinctive product of the reforming process, produced by the dehydrogenation of C6 cycloparaffins, the dehydrocyclization of straight chain paraffins of appropriate chain length (C6) and dealkylation of other aromatics. It is produced in particularly high concentrations in the continuous catalytic reforming process which is currently replacing the conventional cyclic reforming process in the industry. It would be possible to reduce the benzene content of the reformate by a simple fractionation process but because the boiling point of benzene is close to that of other desirable and unobjectionable components of the reformate, this too would lead to a considerable loss in yield.

Therefore, what is needed is a process for selectively removing certain aromatic components contained in a mixture of aromatic hydrocarbons found in a refinery liquid fuel pool so as to reduce the aromatic content of a gasoline pool for environmental reasons and reduce soot formation in a distillate pool.

SUMMARY OF THE INVENTION

A hydrogenating process has now been devised which is capable of selectively removing certain aromatic components in a mixture of aromatic components based on molecular size which are contained in a refinery gasoline or distillate pool thereby decreasing the aromatic content of the refinery gasoline pool thereby reducing aromatic emissions. Decreased aromatic components in the refinery distillate pool results in a decrease in soot production during combustion when kerosene and jet fuels are produced from the distillate pool.

It has now been found that hydrogenating refinery gasoline and distillate feedstocks containing certain aromatic components in a mixture of other aromatic components results in the selective formation of cycloalkanes based on a desired molecular size of the aromatic component. This hydrogenating process comprises a one-stage process utilizing, as a catalyst, a non-acidic, microporous crystalline Pt/ZSM-5 material containing a hydrogenating metal and modifiers such as tin, lead, or indium. During the hydrogenating process, only those aromatic components which can enter the Pt/ZSM-5 modified catalyst are converted to cycloalkanes. Bulkier polyalkyl aromatics too large to enter the catalyst are not converted.

This process generally comprises contacting the feedstock at a temperature between about 100° C. (212° F.) and about 400° C. (752° F.) and a pressure between about atmospheric and 500 psig with a catalyst in the presence of hydrogen, in which the hydrogen-to-feedstock ratio is between about 500 and 2,000 standard cubic feet of hydrogen per barrel of feed. The feedstock is contacted with the catalyst in a fixed bed at a liquid hourly space velocity between about 0.1 and 20.

In a preferred embodiment, the catalyst is used as a hydrofinishing catalyst for the selective conversion of certain aromatics to cycloalkanes in the hydrotreating (HDT) stage of a lube oil hydroprocessing process.

It is therefore an object of this invention to provide a platinum/ZSM-5 zeolite catalyst modified with tin, lead, or indium to selectively hydrogenate certain aromatic hydrocarbons in admixture with other aromatics.

It is another object of this invention to provide for a process for catalytically hydrogenating a gasoline refinery pool to produce a pool reduced in certain aromatic components which selectively enter a Pt/ZSM-5 modified tin, lead, or indium catalyst so as to obtain a gasoline pool that is substantially more environmentally acceptable.

It is yet another object of this invention to provide for a catalytic hydrotreating process which utilizes a distillate refinery pool containing an admixture of aromatic components to produce a distillate refinery pool reduced in aromatic content based on molecular size.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the present process, an aromatic containing fraction obtained from a petroleum refinery stream is contacted with a platinum/ZSM-5 microporous crystalline catalyst modified with tin, lead, or indium in a catalytic hydrofinishing reactor under hydrotreating conditions. The reaction is allowed to continue for a time sufficient to convert selectively certain aromatic components to cycloalkanes. Only those aromatic components which are of a size sufficient to enter into the catalyst are hydrogenated to their cycloalkane components which contain a corresponding number of carbon atoms. Generally, aromatic components which enter the pores of the catalyst will comprise benzene, toluene, and xylenes which are collectively referred to as (BTX). Other representative aromatics of a size sufficient to enter the pores of the catalyst include monoalkylbenzene and beta-alkyl-naphthalene. Bulkier polyalkylaromatics too large to enter the pores of the catalyst are excluded and remained unchanged. A catalytic dewaxing procedure where a ZSM-5 or other aluminosilicate zeolite catalyst is employed that teaches a hydrofinishing step which step can be utilized herein is disclosed in U.S. Pat. No. 4,952,303 which issued to Bortz et al. on Aug. 28, 1990. This patent is hereby incorporated herein by reference.

This process generally comprises contacting the feedstock at a temperature between about 100° C. and about 400° F. and a pressure between about atmospheric and 500 psig with a catalyst in the presence of hydrogen, in which the hydrogen-to-feedstock ratio is between about 500 and 2,000 standard cubic feet of hydrogen per barrel of feed. The feedstock is contacted with the catalyst in a fixed bed at a liquid hourly space velocity between about 0.1 and 20.

The preferred source of the aromatic component containing fraction is a reformate i.e., a refinery stream which has been subjected to catalytic reforming, preferably over a reforming catalyst containing platinum. Other refinery streams containing significant quantities of aromatics and with a suitable boiling range of about C5 to 100° C. (C5 to about 203° C.), usually C5 to 330° F. (C5 to about 165° C.) may, however, be used. Kerosine distilled from the crude unit is an example of a distillate stream from which certain aromatic hydrocarbons can be converted to cycloalkanes when admixed with bulkier polyalkyl aromatics.

Reformates usually contain C6 to C8 aromatic hydrocarbons and C5 to C6 paraffinic hydrocarbons with the aromatic hydrocarbons being constituted mainly by benzene, toluene, xylene and ethyl benzene. Compositions for reformates which may be used in the present process are shown in Table 1 below:

              TABLE 1______________________________________Reformate Composition    Broad    Intermediate                        Narrow______________________________________Specific Gravity      0.72 to 0.88                 0.76 to 0.88                            0.76 to 0.83Boiling Range,°F. 60 to 400  60 to 400  80 to 390°C. 15 to 205  15 to 205  27 to 200Mole %Benzene    5 to 60    5 to 40    10 to 30Toluene    5 to 60    10 to 40   10 to 40C.sub.8 Aromatic.sup.(1)      5 to 60    5 to 50    5 to 15______________________________________ .sup.(1) Xylene and ethyl benzene component.

The composition of a typical reformer stream from a platinum reforming process is given in Table 2 below.

              TABLE 2______________________________________Reformate Composition        Mol. Pct.______________________________________C.sub.4        0.2C.sub.5        15.5Non-arom. C.sub.6          10.2Benzene        25.8Non-arom. C.sub.7          0.2Toluene        34.9C.sub.8 aromatics          10.2C.sub.9 aromatics          3.0______________________________________

As may be seen from the above figures, benzene constitutes a significant proportion of the reformate stream and if no measures are taken to remove it, it will pass into the refinery gasoline pool unchanged. The present method provides a convenient way of converting the benzene to cyclohexanes which are not objectionable environmentally and which conversion also increases the yield of the gasoline pool.

The Catalysts

The catalyst comprises a Group VIII metal and a non-acidic microporous material. The non-acidic microporous material can also be "crystalline" in the sense that it has a unique X-ray diffraction pattern. The X-ray diffraction pattern of ZSM-5 has been described in U.S. Pat. No. 3,702,886 and Re No. 29,948 each of which is incorporated by reference herein. Preferably, the microporous crystalline material contains a modifier selected from the group consisting of tin, indium, or lead. The preferred catalysts are described in allowed U.S. Pat. application Ser. No. 418,377, filed Oct. 6, 1989, and its parent, U.S. Pat. No. 4,990,710, each of which is relied upon and incorporated by reference herein.

The amount of Group VIII metal in the non-acidic catalyst composition employed can range from about 0.05 to 10 weight percent and preferably 0.1 to 5 weight percent of the microporous material. In a preferred embodiment, platinum is the Group VIII metal in the non-acidic catalyst composition. However, the metal can be any Group VIII metals including those of the platinum group (platinum, iridium, and palladium).

The modifier content of the crystalline microporous materials can range from about 0.01 to 20 weight percent. Practically, the modifier content will range from about 0.1 to 10 weight percent.

The crystalline microporous materials of the invention can be medium pore zeolites characterized by Si/Al ratios of at least 10 that have a pore size of about 5 to about 6.5 Angstroms. However, the silica:alumina ratio of the zeolite can be up to 1,000 or greater. In a preferred embodiment the aluminum content of these materials is less than about 1 weight percent and more preferably less than about 0.1 weight percent. Zeolite materials which can be used herein include ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, and MCM-22.

The compositions comprising Group VIII metal-containing catalysts do not exhibit any appreciable acid activity. These catalysts would meet the criteria of non-acidic catalysts described by Davis et al., J. Catal., 15, 363 (1969).

The crystalline microporous material has an X-ray diffraction pattern which corresponds to a zeolite, SAPO, ALPO, etc. The preferred microporous crystalline materials are crystalline in the sense that they are identifiable as isostructural with zeolites by X-ray powder diffraction pattern. Preferred zeolites are those having the structure of ZSM-5.

Incorporation of the modifier and other elements, such as indium, tin, or lead, was accomplished during synthesis of the high silica/ alumina ZSM-5 zeolites. Platinum was incorporated via ion-exchange with Pt(NH3)4 Cl2, followed by calcination in air to 350° C. Crystal sizes were all about 1 micron.

Competitive hydrogenation of equimolar mixtures of ortho- and para-xylene was conducted in excess hydrogen at 300 psig and 250-325° C. Liquid products were collected in a cold trap and analyzed on a DB-1 capillary column of a gas chromatographic apparatus. All products were identified by comparison to authentic samples.

In a preferred embodiment the pore size of the microporous crystalline silicates ranges from about 5 to about 6.5 Angstroms. For a more complete description of these zeolites, reference is made to the The Atlas Of Zeolite Structure Types (1992) by W. M. Meier and D. H. Olson published by Butterworth Publishers. In a preferred embodiment the microporous crystalline material exhibits the structure of ZSM-5, by X-ray diffraction pattern. When as the in embodiments herein, the crystalline material exhibits an X-ray diffraction pattern of a zeolite, at least some of the hydrogenation metal may be intrazeolitic, that is, some of that metal is within the pore structure of the crystal, although some of that metal can be on the surface of the crystal. A test for determining whether, for example, Pt is intrazeolitic or extrazeolitic in the case of ZSM-5 is reported by R. M. Dessau, J. Catal. 89, 520 (1984). The test is based on the selective hydrogenation of olefins.

The methods of synthesizing these preferred materials are described in U.S. Pat. No. 4,990,710 which is relied upon and incorporated by reference herein.

The non-acidic, crystalline, microporous, Group VIII metal containing materials used in the invention can be combined with a matrix or binder material to render them attrition resistant and more resistant to the severity of the conditions to which they will be exposed during use in hydrocarbon conversion applications. The combined compositions can contain 1 to 99 weight percent of the materials of the invention based on the combined weight of the matrix (binder) and material of the invention. The relative proportions of finely divided crystalline material and inorganic oxide gel matrix vary widely, with the crystal content ranging from about 1 to about 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight percent of the composite. When used with a matrix or binder, the catalyst of the invention will preferably be combined with non-acidic matrix or binder materials. A preferred matrix or binder material would be silica or titania.

The catalysts may be regenerated by conventional techniques including high pressure hydrogen treatment and combustion of coke on the catalyst with an oxygen-containing gas.

The competitive hydrogenation of an equimolar mixture of ortho- and para-xylene to dimethylcyclohexanes was investigated at 325° C. (617° F.) and 300 psig. The yields (mol %) of the various dimethylcyclohexanes (DMCH) produced, 1,4-DMCH from para-xylene and 1,2-DMCH from ortho-xylene, as well as the ratio of these products are shown in Table 3 below:

              TABLE 3______________________________________Catalyst tr-1,4   cis-1,4 tr-1,2 cis-1,2                                  1,4/1,2______________________________________Non-selectivePt/Si-ZSM-5    18.2     8.0     13.7   6.6   1.3Pt/Ti-ZSM-5    8.5      6.2     6.0    5.5   1.3Pt/Zr-ZSM-5    7.9      8.8     4.1    10.3  1.2Pt/[B]zeolite.sup.a    10.6     7.6     7.0    6.7   1.3betaSelectivePt/Sn-ZSM-5    28.2     10.9    1.08   0.32  28Pt/Pb-ZSM-5    16.0     6.7     0.36   0.12  47Pt/In-ZSM-5    9.9      5.0     2.9    2.7   2.7______________________________________ .sup.a At 250° C. (482° F.), 75 psig.

Shape selective preferential hydrogenation of para-xylene was observed for tin-, lead-, and indium-modified Pt/ZSM-5 catalysts.

The competitive hydrogenation of an equimolar mixture of benzene, toluene, and para-xylene was investigated at 250° C. and 300 psig over both a para-selective Pt/[Sn]ZSM-5. The results are shown in Table 4, below:

              TABLE 4______________________________________Hydrogenation (Hydr) of BTXCatalyst  % Benz Hydr                % Tol Hydr % Para-Xyl Hydr______________________________________Pt/[Sn]ZSM-5     69         44         17______________________________________

In both cases, the order of reactivity was benzene>toluene>para-xylene. This order contrasts with that observed over sulfided Ni/W on alumina (J. L. LePage in a publication entitled "Applied Heterogeneous Catalysis", published by Gulf Publishing Co., Houston, Tex., 1987 on page 371).

Shape selective hydrogenation of para-xylene relative to ortho-xylene was achieved over tin, lead, and indium modified Pt/ZSM-5 catalysts. The failure to observe similar selectivities for unmodified Pt/ZSM-5 catalysts demonstrates the anchoring effect of these modifiers in suppressing platinum migration out of zeolitic channels.

Obviously, many other variations and modifications of this invention as previously set forth may be made without departing from the spirit and scope of this invention as those skilled in the art readily understand. Such variations and modifications are considered part of this invention and within the purview and scope of the appended claims.

Claims (13)

What is claimed:
1. A process for the shape selective preferential hydrogenation of certain aromatic components in a mixture of aromatic hydrocarbonaceous components based on molecular size comprising:
hydrotreating a feed containing a mixture of aromatic hydrocarbonaceous components under hydrotreating conditions at a temperature of from about 100° C. to about 325° C. in the presence of a non-acidic crystalline microporous ZSM-5 catalyst containing a Group VIII metal modified with a metal selected from a member of the group consisting of tin, lead, or indium for a time sufficient to convert aromatic components having a molecular size sufficient to pass through said catalyst to cycloalkanes thereby producing an effluent with a reduced aromatic content.
2. The process as recited in claim 1 where the Group VIII metal is platinum modified with tin.
3. The process as recited in claim 1 where the feed is a refinery reformate stream.
4. The process as recited in claim 1 where the crystalline microporous catalyst has a crystalline structure that contains aluminum in the amount of less than about 0.1 weight %.
5. The process as recited in claim 1 where the feed is a refinery distillate stream and the effluent therefrom has reduced soot formation upon combustion when compared to the feed prior to hydrotreating.
6. The process as recited in claim 1 where the Group VIII metal is platinum.
7. The process as recited in claim 1 where the feed is a refinery reformate stream or a distillate stream and a converted aromatic component is benzene thus causing a reduction in the benzene content of said stream.
8. The process as recited in claim 1 where hydrotreating is conducted at a liquid hourly space velocity of from about 0.5 to about 20, a pressure of about atmospheric to about 500 psig, a temperature of from about 100° to about 325° C., and a once-through hydrogen circulation rate of about 500 to about 2,000 standard cubic feed per barrel of feed.
9. A process for the shape selective preferential hydrogenation of certain aromatic components in a reformate containing a mixture of aromatic hydrocarbonaceous components based on molecular size comprising:
hydrotreating a feed containing a mixture of aromatic hydrocarbonaceous components under hydrotreating conditions at a temperature of from about 100° C. to about 325° C. in the presence of a non-acidic crystalline microporous ZSM-5 catalyst containing platinum modified with tin for a time sufficient to convert aromatic components having a molecular size sufficient to pass through said catalyst to cycloalkanes thereby producing a reformate effluent with a reduced aromatic content.
10. The process as recited in claim 9 where the crystalline microporous catalyst has a crystalline structure that contains aluminum in the amount of less than about 0.1 weight %.
11. The process as recited in claim 9 where the feed is a refinery distillate stream and the effluent therefrom has reduced soot formation upon combustion when compared to the feed prior to hydrotreating.
12. The process as recited in claim 9 where the feed is a refinery reformate stream or a distillate stream and a converted aromatic component is benzene thus causing a reduction in the benzene content of said stream.
13. The process as recited in claim 9 where hydrotreating is conducted at a liquid hourly space velocity of from about 0.5 to about 20, a pressure of about atmospheric to about 500 psig, a temperature of from about 100° to about 325° C., and a once-through hydrogen circulation rate of about 500 to about 2,000 standard cubic feet per barrel of feed.
US07992668 1992-12-18 1992-12-18 Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts Expired - Fee Related US5350504A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US07992668 US5350504A (en) 1992-12-18 1992-12-18 Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts
PCT/US1994/008100 WO1996002612A1 (en) 1992-12-18 1994-07-19 Shape selective hydrogenation of aromatics

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07992668 US5350504A (en) 1992-12-18 1992-12-18 Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts
PCT/US1994/008100 WO1996002612A1 (en) 1992-12-18 1994-07-19 Shape selective hydrogenation of aromatics

Publications (1)

Publication Number Publication Date
US5350504A true US5350504A (en) 1994-09-27

Family

ID=25538602

Family Applications (1)

Application Number Title Priority Date Filing Date
US07992668 Expired - Fee Related US5350504A (en) 1992-12-18 1992-12-18 Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts

Country Status (1)

Country Link
US (1) US5350504A (en)

Cited By (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855767A (en) * 1994-09-26 1999-01-05 Star Enterprise Hydrorefining process for production of base oils
US20050020718A1 (en) * 2001-09-25 2005-01-27 Claudius Gosse Plasticised polyvinyl chloride
US20100029995A1 (en) * 2008-07-31 2010-02-04 Johnston Victor J Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
US20100029993A1 (en) * 2008-07-31 2010-02-04 Johnston Victor J Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst
US20100029980A1 (en) * 2008-07-31 2010-02-04 Johnston Victor J Direct and selective production of ethyl acetate from acetic acid utilizing a bimetal supported catalyst
US20100121114A1 (en) * 2008-07-31 2010-05-13 Heiko Weiner Tunable catalyst gas phase hydrogenation of carboxylic acids
US20100168466A1 (en) * 2008-12-31 2010-07-01 Johnston Victor J Integrated process for the production of vinyl acetate from acetic acid via acetaldehyde
US20100197486A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethyl acetate from acetic acid
US20100197485A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethanol from acetic acid
US20100197985A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Processes for making ethanol from acetic acid
US20110098513A1 (en) * 2009-10-26 2011-04-28 Celanese International Corporation Process for making diethyl ether from acetic acid
WO2011053367A1 (en) * 2009-10-26 2011-05-05 Celanese International Corporation Catalysts for making ethyl acetate from acetic acid
WO2011090872A2 (en) * 2010-01-19 2011-07-28 Uop Llc Process for increasing methyl to phenyl mole ratios and reducing benzene content in a motor fuel product
US20110190117A1 (en) * 2010-02-01 2011-08-04 Celanese International Corporation Processes for making tin-containing catalysts
US8222466B2 (en) 2010-02-02 2012-07-17 Celanese International Corporation Process for producing a water stream from ethanol production
US8304586B2 (en) 2010-02-02 2012-11-06 Celanese International Corporation Process for purifying ethanol
US8309773B2 (en) 2010-02-02 2012-11-13 Calanese International Corporation Process for recovering ethanol
US8314272B2 (en) 2010-02-02 2012-11-20 Celanese International Corporation Process for recovering ethanol with vapor separation
US8338650B2 (en) 2008-07-31 2012-12-25 Celanese International Corporation Palladium catalysts for making ethanol from acetic acid
US8344186B2 (en) 2010-02-02 2013-01-01 Celanese International Corporation Processes for producing ethanol from acetaldehyde
US8350098B2 (en) 2011-04-04 2013-01-08 Celanese International Corporation Ethanol production from acetic acid utilizing a molybdenum carbide catalyst
US8450535B2 (en) 2009-07-20 2013-05-28 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US8455702B1 (en) 2011-12-29 2013-06-04 Celanese International Corporation Cobalt and tin catalysts for producing ethanol
US8460405B2 (en) 2010-02-02 2013-06-11 Celanese International Corporation Ethanol compositions
US8487143B2 (en) 2008-07-31 2013-07-16 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US8536383B1 (en) 2012-03-14 2013-09-17 Celanese International Corporation Rhodium/tin catalysts and processes for producing ethanol
US8536382B2 (en) 2011-10-06 2013-09-17 Celanese International Corporation Processes for hydrogenating alkanoic acids using catalyst comprising tungsten
US8541633B2 (en) 2010-02-02 2013-09-24 Celanese International Corporation Processes for producing anhydrous ethanol compositions
US8546622B2 (en) 2008-07-31 2013-10-01 Celanese International Corporation Process for making ethanol from acetic acid using acidic catalysts
US8569551B2 (en) 2010-05-07 2013-10-29 Celanese International Corporation Alcohol production process integrating acetic acid feed stream comprising water from carbonylation process
US8569549B2 (en) 2010-02-02 2013-10-29 Celanese International Corporation Catalyst supports having crystalline support modifiers
US8575406B2 (en) 2011-12-22 2013-11-05 Celanese International Corporation Catalysts having promoter metals and process for producing ethanol
US8637714B2 (en) 2008-07-31 2014-01-28 Celanese International Corporation Process for producing ethanol over catalysts containing platinum and palladium
US8658843B2 (en) 2011-10-06 2014-02-25 Celanese International Corporation Hydrogenation catalysts prepared from polyoxometalate precursors and process for using same to produce ethanol while minimizing diethyl ether formation
US8668750B2 (en) 2010-02-02 2014-03-11 Celanese International Corporation Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels
US8680321B2 (en) 2009-10-26 2014-03-25 Celanese International Corporation Processes for making ethanol from acetic acid using bimetallic catalysts
US8680317B2 (en) 2008-07-31 2014-03-25 Celanese International Corporation Processes for making ethyl acetate from acetic acid
US8680342B2 (en) 2010-05-07 2014-03-25 Celanese International Corporation Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water
US8680343B2 (en) 2010-02-02 2014-03-25 Celanese International Corporation Process for purifying ethanol
US8703868B2 (en) 2011-11-28 2014-04-22 Celanese International Corporation Integrated process for producing polyvinyl alcohol or a copolymer thereof and ethanol
US8728179B2 (en) 2010-02-02 2014-05-20 Celanese International Corporation Ethanol compositions
US8747492B2 (en) 2010-02-02 2014-06-10 Celanese International Corporation Ethanol/fuel blends for use as motor fuels
US8754267B2 (en) 2010-05-07 2014-06-17 Celanese International Corporation Process for separating acetaldehyde from ethanol-containing mixtures
WO2014092928A1 (en) * 2012-12-14 2014-06-19 Uop Llc Methods and apparatuses for increasing alkyl-cyclopentane concentrations in aromatic-rich streams
US8772553B2 (en) 2012-10-26 2014-07-08 Celanese International Corporation Hydrogenation reaction conditions for producing ethanol
US8802588B2 (en) 2012-01-23 2014-08-12 Celanese International Corporation Bismuth catalyst composition and process for manufacturing ethanol mixture
US8858659B2 (en) 2010-02-02 2014-10-14 Celanese International Corporation Processes for producing denatured ethanol
US8865609B2 (en) 2012-01-06 2014-10-21 Celanese International Corporation Hydrogenation catalysts
US8907142B2 (en) 2011-12-29 2014-12-09 Celanese International Corporation Process for promoting catalyst activity for ethyl acetate conversion
US8927786B2 (en) 2012-03-13 2015-01-06 Celanese International Corporation Ethanol manufacturing process over catalyst having improved radial crush strength
US8932372B2 (en) 2010-02-02 2015-01-13 Celanese International Corporation Integrated process for producing alcohols from a mixed acid feed
US8981164B2 (en) 2012-01-06 2015-03-17 Celanese International Corporation Cobalt and tin hydrogenation catalysts
US9000234B2 (en) 2011-12-22 2015-04-07 Celanese International Corporation Calcination of modified support to prepare hydrogenation catalysts
US9024086B2 (en) 2012-01-06 2015-05-05 Celanese International Corporation Hydrogenation catalysts with acidic sites
US9050585B2 (en) 2012-02-10 2015-06-09 Celanese International Corporation Chemisorption of ethyl acetate during hydrogenation of acetic acid to ethanol
US9073042B2 (en) 2012-03-14 2015-07-07 Celanese International Corporation Acetic acid hydrogenation over a group VIII metal calcined catalyst having a secondary promoter
US9079172B2 (en) 2012-03-13 2015-07-14 Celanese International Corporation Promoters for cobalt-tin catalysts for reducing alkanoic acids
US9126194B2 (en) 2012-02-29 2015-09-08 Celanese International Corporation Catalyst having support containing tin and process for manufacturing ethanol
US9233899B2 (en) 2011-12-22 2016-01-12 Celanese International Corporation Hydrogenation catalysts having an amorphous support
US9333496B2 (en) 2012-02-29 2016-05-10 Celanese International Corporation Cobalt/tin catalyst for producing ethanol

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3702886A (en) * 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
USRE29948E (en) * 1973-11-02 1979-03-27 Mobil Oil Corporation Crystalline silicates and catalytic conversion of organic compounds therewith
US4175033A (en) * 1976-05-06 1979-11-20 Uop Inc. Hydroprocessing of hydrocarbons over nickel, moly, platinum catalyst
US4952303A (en) * 1985-07-10 1990-08-28 Mobil Oil Corp. Process for preparing a very high quality lube base stock oil
US4966880A (en) * 1989-07-03 1990-10-30 Exxon Research & Engineering Company Novel platinum-tin-alumina reforming catalysts
US4990710A (en) * 1988-06-24 1991-02-05 Mobil Oil Corporation Tin-containing microporous crystalline materials and their use as dehydrogenation, dehydrocyclization and reforming catalysts
US5032561A (en) * 1988-09-29 1991-07-16 Teijin Petrochemical Industries, Ltd. Catalyst composition for cracking non-aromatic hydrocarbons and isomerizing C8-aromatic hydrocarbons

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3702886A (en) * 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
USRE29948E (en) * 1973-11-02 1979-03-27 Mobil Oil Corporation Crystalline silicates and catalytic conversion of organic compounds therewith
US4175033A (en) * 1976-05-06 1979-11-20 Uop Inc. Hydroprocessing of hydrocarbons over nickel, moly, platinum catalyst
US4952303A (en) * 1985-07-10 1990-08-28 Mobil Oil Corp. Process for preparing a very high quality lube base stock oil
US4990710A (en) * 1988-06-24 1991-02-05 Mobil Oil Corporation Tin-containing microporous crystalline materials and their use as dehydrogenation, dehydrocyclization and reforming catalysts
US5032561A (en) * 1988-09-29 1991-07-16 Teijin Petrochemical Industries, Ltd. Catalyst composition for cracking non-aromatic hydrocarbons and isomerizing C8-aromatic hydrocarbons
US4966880A (en) * 1989-07-03 1990-10-30 Exxon Research & Engineering Company Novel platinum-tin-alumina reforming catalysts

Cited By (101)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5855767A (en) * 1994-09-26 1999-01-05 Star Enterprise Hydrorefining process for production of base oils
US20050020718A1 (en) * 2001-09-25 2005-01-27 Claudius Gosse Plasticised polyvinyl chloride
US7297738B2 (en) 2001-09-25 2007-11-20 Exxonmobil Chemical Patents Inc. Plasticized polyvinyl chloride
US7413813B2 (en) 2001-09-25 2008-08-19 Exxonmobil Chemical Patents Inc. Plasticised polyvinyl chloride
US7585571B2 (en) 2001-09-25 2009-09-08 Exxonmobil Chemical Patents Inc. Plasticised polyvinyl chloride
US7855340B2 (en) 2001-09-25 2010-12-21 Exxonmobil Chemical Patents Inc. Plasticised polyvinyl chloride
US8546622B2 (en) 2008-07-31 2013-10-01 Celanese International Corporation Process for making ethanol from acetic acid using acidic catalysts
US20100029980A1 (en) * 2008-07-31 2010-02-04 Johnston Victor J Direct and selective production of ethyl acetate from acetic acid utilizing a bimetal supported catalyst
US20100121114A1 (en) * 2008-07-31 2010-05-13 Heiko Weiner Tunable catalyst gas phase hydrogenation of carboxylic acids
US8889923B2 (en) 2008-07-31 2014-11-18 Celanese International Corporation Synthesis of ethanol from biomass
US20100197486A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethyl acetate from acetic acid
US20100197485A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Catalysts for making ethanol from acetic acid
US20100029993A1 (en) * 2008-07-31 2010-02-04 Johnston Victor J Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst
US7816565B2 (en) 2008-07-31 2010-10-19 Celanese International Corporation Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst
US7820852B2 (en) 2008-07-31 2010-10-26 Celanese International Corporation Direct and selective production of ethyl acetate from acetic acid utilizing a bimetal supported catalyst
US20100029995A1 (en) * 2008-07-31 2010-02-04 Johnston Victor J Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
US7863489B2 (en) 2008-07-31 2011-01-04 Celanese International Corporation Direct and selective production of ethanol from acetic acid utilizing a platinum/tin catalyst
US20110004026A1 (en) * 2008-07-31 2011-01-06 Celanese International Corporation Direct and Selective Production of Acetaldehyde from Acetic Acid Utilizing a Supported Metal Catalyst
US20110004033A1 (en) * 2008-07-31 2011-01-06 Celanese International Corporation Direct and Selective Production of Ethanol from Acetic Acid Utilizing a Platinum/ Tin Catalyst
US8680317B2 (en) 2008-07-31 2014-03-25 Celanese International Corporation Processes for making ethyl acetate from acetic acid
US8669400B2 (en) 2008-07-31 2014-03-11 Celanese International Corporation Direct and selective production of ethanol from acetic acid utilizing a platinum/ tin catalyst
US8637714B2 (en) 2008-07-31 2014-01-28 Celanese International Corporation Process for producing ethanol over catalysts containing platinum and palladium
US8993815B2 (en) 2008-07-31 2015-03-31 Celanese International Corporation Process for vapor phase hydrogenation
US7994368B2 (en) 2008-07-31 2011-08-09 Celanese International Corporation Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst
US9024087B2 (en) 2008-07-31 2015-05-05 Celanese International Corporation Process for making ethanol from acetic acid using acidic catalysts
US8071821B2 (en) 2008-07-31 2011-12-06 Celanese International Corporation Direct and selective production of ethanol from acetic acid utilizing a platinum/ tin catalyst
US8080694B2 (en) 2008-07-31 2011-12-20 Celanese International Corporation Catalyst for gas phase hydrogenation of carboxylic acids having a support modified with a reducible metal oxide
US8338650B2 (en) 2008-07-31 2012-12-25 Celanese International Corporation Palladium catalysts for making ethanol from acetic acid
US20100197985A1 (en) * 2008-07-31 2010-08-05 Celanese International Corporation Processes for making ethanol from acetic acid
US8853122B2 (en) 2008-07-31 2014-10-07 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US8227644B2 (en) 2008-07-31 2012-07-24 Celanese International Corporation Direct and selective production of acetaldehyde from acetic acid utilizing a supported metal catalyst
US9040443B2 (en) 2008-07-31 2015-05-26 Celanese International Corporation Catalysts for making ethanol from acetic acid
US8309772B2 (en) 2008-07-31 2012-11-13 Celanese International Corporation Tunable catalyst gas phase hydrogenation of carboxylic acids
US8501652B2 (en) 2008-07-31 2013-08-06 Celanese International Corporation Catalysts for making ethanol from acetic acid
US8487143B2 (en) 2008-07-31 2013-07-16 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US8461395B2 (en) 2008-07-31 2013-06-11 Celanese International Corporation Synthesis of acetaldehyde from a carbon source
US8471075B2 (en) 2008-07-31 2013-06-25 Celanese International Corporation Processes for making ethanol from acetic acid
US8802904B2 (en) 2008-07-31 2014-08-12 Celanese International Corporation Processes for making ethanol from acetic acid
US8754270B2 (en) 2008-07-31 2014-06-17 Celanese International Corporation Process for vapor phase hydrogenation
US8178715B2 (en) 2008-12-31 2012-05-15 Celanese International Corporation Integrated process for the production of vinyl acetate from acetic acid via acetaldehyde
US20100168466A1 (en) * 2008-12-31 2010-07-01 Johnston Victor J Integrated process for the production of vinyl acetate from acetic acid via acetaldehyde
US8450535B2 (en) 2009-07-20 2013-05-28 Celanese International Corporation Ethanol production from acetic acid utilizing a cobalt catalyst
US8680321B2 (en) 2009-10-26 2014-03-25 Celanese International Corporation Processes for making ethanol from acetic acid using bimetallic catalysts
US8710277B2 (en) 2009-10-26 2014-04-29 Celanese International Corporation Process for making diethyl ether from acetic acid
US20110098513A1 (en) * 2009-10-26 2011-04-28 Celanese International Corporation Process for making diethyl ether from acetic acid
WO2011053367A1 (en) * 2009-10-26 2011-05-05 Celanese International Corporation Catalysts for making ethyl acetate from acetic acid
WO2011090872A2 (en) * 2010-01-19 2011-07-28 Uop Llc Process for increasing methyl to phenyl mole ratios and reducing benzene content in a motor fuel product
WO2011090872A3 (en) * 2010-01-19 2011-11-17 Uop Llc Process for increasing methyl to phenyl mole ratios and reducing benzene content in a motor fuel product
US8211821B2 (en) 2010-02-01 2012-07-03 Celanese International Corporation Processes for making tin-containing catalysts
US8569203B2 (en) 2010-02-01 2013-10-29 Celanese International Corporation Processes for making tin-containing catalysts
US20110190117A1 (en) * 2010-02-01 2011-08-04 Celanese International Corporation Processes for making tin-containing catalysts
US8541633B2 (en) 2010-02-02 2013-09-24 Celanese International Corporation Processes for producing anhydrous ethanol compositions
US8222466B2 (en) 2010-02-02 2012-07-17 Celanese International Corporation Process for producing a water stream from ethanol production
US8569549B2 (en) 2010-02-02 2013-10-29 Celanese International Corporation Catalyst supports having crystalline support modifiers
US8304586B2 (en) 2010-02-02 2012-11-06 Celanese International Corporation Process for purifying ethanol
US8309773B2 (en) 2010-02-02 2012-11-13 Calanese International Corporation Process for recovering ethanol
US8653308B2 (en) 2010-02-02 2014-02-18 Celanese International Corporation Process for utilizing a water stream in a hydrolysis reaction to form ethanol
US8932372B2 (en) 2010-02-02 2015-01-13 Celanese International Corporation Integrated process for producing alcohols from a mixed acid feed
US8668750B2 (en) 2010-02-02 2014-03-11 Celanese International Corporation Denatured fuel ethanol compositions for blending with gasoline or diesel fuel for use as motor fuels
US8314272B2 (en) 2010-02-02 2012-11-20 Celanese International Corporation Process for recovering ethanol with vapor separation
US8344186B2 (en) 2010-02-02 2013-01-01 Celanese International Corporation Processes for producing ethanol from acetaldehyde
US8460405B2 (en) 2010-02-02 2013-06-11 Celanese International Corporation Ethanol compositions
US9051238B2 (en) 2010-02-02 2015-06-09 Celanese International Corporation Process for recovering ethanol
US8680343B2 (en) 2010-02-02 2014-03-25 Celanese International Corporation Process for purifying ethanol
US8704015B2 (en) 2010-02-02 2014-04-22 Celanese International Corporation Process for recovering ethanol
US8704014B2 (en) 2010-02-02 2014-04-22 Celansese International Corporation Process for purifying ethanol
US8858659B2 (en) 2010-02-02 2014-10-14 Celanese International Corporation Processes for producing denatured ethanol
US8426652B2 (en) 2010-02-02 2013-04-23 Celanese International Corporation Processes for producing ethanol from acetaldehyde
US8728179B2 (en) 2010-02-02 2014-05-20 Celanese International Corporation Ethanol compositions
US8747492B2 (en) 2010-02-02 2014-06-10 Celanese International Corporation Ethanol/fuel blends for use as motor fuels
US9447005B2 (en) 2010-02-02 2016-09-20 Celanese International Corporation Processes for producing anhydrous ethanol compositions
US8399719B2 (en) 2010-02-02 2013-03-19 Celanese International Corporation Process for producing a water stream from ethanol production
US8680342B2 (en) 2010-05-07 2014-03-25 Celanese International Corporation Process for recovering alcohol produced by hydrogenating an acetic acid feed stream comprising water
US8569551B2 (en) 2010-05-07 2013-10-29 Celanese International Corporation Alcohol production process integrating acetic acid feed stream comprising water from carbonylation process
US8754267B2 (en) 2010-05-07 2014-06-17 Celanese International Corporation Process for separating acetaldehyde from ethanol-containing mixtures
US8350098B2 (en) 2011-04-04 2013-01-08 Celanese International Corporation Ethanol production from acetic acid utilizing a molybdenum carbide catalyst
US8658843B2 (en) 2011-10-06 2014-02-25 Celanese International Corporation Hydrogenation catalysts prepared from polyoxometalate precursors and process for using same to produce ethanol while minimizing diethyl ether formation
US8536382B2 (en) 2011-10-06 2013-09-17 Celanese International Corporation Processes for hydrogenating alkanoic acids using catalyst comprising tungsten
US8703868B2 (en) 2011-11-28 2014-04-22 Celanese International Corporation Integrated process for producing polyvinyl alcohol or a copolymer thereof and ethanol
US9000234B2 (en) 2011-12-22 2015-04-07 Celanese International Corporation Calcination of modified support to prepare hydrogenation catalysts
US8575406B2 (en) 2011-12-22 2013-11-05 Celanese International Corporation Catalysts having promoter metals and process for producing ethanol
US9233899B2 (en) 2011-12-22 2016-01-12 Celanese International Corporation Hydrogenation catalysts having an amorphous support
US8907142B2 (en) 2011-12-29 2014-12-09 Celanese International Corporation Process for promoting catalyst activity for ethyl acetate conversion
US8455702B1 (en) 2011-12-29 2013-06-04 Celanese International Corporation Cobalt and tin catalysts for producing ethanol
US8975200B2 (en) 2012-01-06 2015-03-10 Celanese International Corporation Hydrogenation catalysts with cobalt-modified supports
US8981164B2 (en) 2012-01-06 2015-03-17 Celanese International Corporation Cobalt and tin hydrogenation catalysts
US8865609B2 (en) 2012-01-06 2014-10-21 Celanese International Corporation Hydrogenation catalysts
US9308523B2 (en) 2012-01-06 2016-04-12 Celanese International Corporation Hydrogenation catalysts with cobalt-modified supports
US9381500B2 (en) 2012-01-06 2016-07-05 Celanese International Corporation Process for producing ethanol using hydrogenation catalysts
US9024086B2 (en) 2012-01-06 2015-05-05 Celanese International Corporation Hydrogenation catalysts with acidic sites
US8802588B2 (en) 2012-01-23 2014-08-12 Celanese International Corporation Bismuth catalyst composition and process for manufacturing ethanol mixture
US9050585B2 (en) 2012-02-10 2015-06-09 Celanese International Corporation Chemisorption of ethyl acetate during hydrogenation of acetic acid to ethanol
US9333496B2 (en) 2012-02-29 2016-05-10 Celanese International Corporation Cobalt/tin catalyst for producing ethanol
US9126194B2 (en) 2012-02-29 2015-09-08 Celanese International Corporation Catalyst having support containing tin and process for manufacturing ethanol
US9079172B2 (en) 2012-03-13 2015-07-14 Celanese International Corporation Promoters for cobalt-tin catalysts for reducing alkanoic acids
US8927786B2 (en) 2012-03-13 2015-01-06 Celanese International Corporation Ethanol manufacturing process over catalyst having improved radial crush strength
US9486781B2 (en) 2012-03-13 2016-11-08 Celanese International Corporation Ethanol manufacturing process over catalyst having improved radial crush strength
US8536383B1 (en) 2012-03-14 2013-09-17 Celanese International Corporation Rhodium/tin catalysts and processes for producing ethanol
US9073042B2 (en) 2012-03-14 2015-07-07 Celanese International Corporation Acetic acid hydrogenation over a group VIII metal calcined catalyst having a secondary promoter
US8772553B2 (en) 2012-10-26 2014-07-08 Celanese International Corporation Hydrogenation reaction conditions for producing ethanol
WO2014092928A1 (en) * 2012-12-14 2014-06-19 Uop Llc Methods and apparatuses for increasing alkyl-cyclopentane concentrations in aromatic-rich streams

Similar Documents

Publication Publication Date Title
US4402866A (en) Aging resistance shape selective catalyst with enhanced activity
US5576256A (en) Hydroprocessing scheme for production of premium isomerized light gasoline
US4518485A (en) Hydrotreating/isomerization process to produce low pour point distillate fuels and lubricating oil stocks
US3894938A (en) Catalytic dewaxing of gas oils
US4645586A (en) Reforming process
US5882505A (en) Conversion of fisher-tropsch waxes to lubricants by countercurrent processing
US4517306A (en) Composition and a method for its use in dehydrocyclization of alkanes
US4457832A (en) Combination catalytic reforming-isomerization process for upgrading naphtha
US3770614A (en) Split feed reforming and n-paraffin elimination from low boiling reformate
US4913797A (en) Catalyst hydrotreating and dewaxing process
US5011593A (en) Catalytic hydrodesulfurization
US3928174A (en) Combination process for producing LPG and aromatic rich material from naphtha
US5055633A (en) Adsorption and isomerization of normal and mono-methyl paraffins
US4097367A (en) Conversion of olefinic naphtha
US4447316A (en) Composition and a method for its use in dehydrocyclization of alkanes
US4211640A (en) Process for the treatment of olefinic gasoline
US5270272A (en) Sulfur removal from molecular-sieve catalyst
US4435283A (en) Method of dehydrocyclizing alkanes
US5865986A (en) Hydrocarbon conversion
Maxwell Zeolite catalysis in hydroprocessing technology
US5463155A (en) Upgrading of cyclic naphthas
US4614834A (en) Dehydrocyclization with nonacidic L zeolite
US3549515A (en) Hydrocracking process for high end point feeds
US4954241A (en) Two stage hydrocarbon conversion process
US5055634A (en) Adsorption and isomerization of normal and mono-methyl paraffins

Legal Events

Date Code Title Description
AS Assignment

Owner name: MOBIL OIL CORPORATION, VIRGINIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:DESSAU, RALPH M.;REEL/FRAME:006371/0154

Effective date: 19921216

REMI Maintenance fee reminder mailed
FP Expired due to failure to pay maintenance fee

Effective date: 19980927

FPAY Fee payment

Year of fee payment: 4

SULP Surcharge for late payment
PRDP Patent reinstated due to the acceptance of a late maintenance fee

Effective date: 19990709

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Expired due to failure to pay maintenance fee

Effective date: 20020927